Water-dispersible granular agricultural compositions made by heat extrusion

ABSTRACT

Rapidly disintegrating water-soluble or water-dispersible granular compositions are made by extruding a premix through a die or screen at elevated temperature. The extruded composition is chopped or milled to form a granular product. The compositions contain one or more water-soluble ingredients which soften or melt at elevated temperatures. No water is added in the process thereby eliminating the need for drying.

This application has been filed under 35 USC 371 as a national phase application of PCT/US92/01262, filed Feb. 27, 1992, which was a continuation of Ser. No. 07/662,698, filed Mar. 1, 1991, now abandoned.

BACKGROUND OF THE INVENTION

The present invention relates to water-dispersible granular compositions comprising active ingredients of value in agriculture.

It is advantageous to formulate active pesticides as water-dispersible compositions which can be readily mixed with water and applied by means of a spraying apparatus to a locus to be protected. It is also advantageous that such granular compositions can be readily dispersed or dissolved in water. It is also advantageous that the granular compositions have good attrition resistance, uniform size granules and uniform bulk density.

World Patent WO 89/00079 discloses an extrusion process to make water-dispersible granules of agricultural chemicals in which water is added to make an extrudable wet mix. The extrudate is rolled to break the product down to granules and then optionally dried.

U.S. Pat. No. 4,065,289 discloses a herbicidal composition containing a plant fertilizer component and a herbicide component which is extruded through a die at 70° C.-145° C. The herbicide component acts as a lubricant to permit ready extrusion and to form a coherent extrudate.

SUMMARY OF THE INVENTION

The present invention is directed to rapidly disintegrating water-dispersible granular agricultural compositions comprising by weight based on the total weight of the composition:

1) 0.01-90% of one or more active ingredients;

2) 1-60% of one or more water-soluble diluents;

3) 0-30% of one or more water-soluble heat activated binders that melt at temperatures between 40°-120° C.; and

4) two or more additives selected from the group consisting of:

a) 0-10% anticaking agent(s);

b) 0-10% chemical stabilizer(s);

c) 0-20% gas generating agents;

d) 0.1-10% wicking or swelling disintegrant(s);

e) 0.1-20% dispersant(s);

f) 0-5% wetting agent(s); and

g) 0-80% inert filler(s).

The sum of all ingredients in a composition is 100%.

The invention is also directed to a process for preparing the compositions of the invention, said process comprising extruding a premix through a die or screen at elevated temperature without using any water. Accordingly, the process of the invention comprises extruding a dry premix comprising by weight based on the total weight of the composition:

1) 0.01-90% of one or more active ingredients;

2) 1-60% of one or more water-soluble diluents;

3) 0-30% of one or more water-soluble heat activated binders that melt at temperatures between 40°-120° C.; and

4) two or more additives selected from the group consisting of:

(a) 0-10% anticaking agent (s);

(b) 0-10% chemical stabilizer (s);

(c) 0-20% gas generating agents;

(d) 0.1-10% wicking or swelling disintegrant (s);

(e) 0.1-20% dispersant (s);

(f) 0-5% wetting agent (s); and

(g) 0-80% inert filler(s);

through a die or screen at a temperature from 50° C. to 130° C. and chopping or milling the extruded material to form uniform granules.

The active ingredient is at least one chemical used for crop protection or plant growth regulation or pesticide. More specifically, ingredients are selected from the class of herbicides, fungicides, bactericides, insecticides, insect antifeedants, acaricides, miticides, nematocides, and plant growth regulants.

The preferred compositions of the invention are:

1. The composition of the general formula wherein the active ingredient(s) comprise 0.03-80%, the heat activated binder(s) comprise 1-15% and the water-soluble diluent(s) comprise 1-40% by weight based on the total weight of the composition.

2. The composition of Preferred 1 wherein the active ingredient(s) comprise 10-70% by weight.

3. The composition of Preferred 2 wherein the water soluble diluent is urea, ethylurea, sorbitol, lactose or sodium acetate trihydrate and mixtures of the foregoing.

4. The composition of Preferred 3 wherein the heat activated binder(s) is selected from the classes consisting of polyethoxylated alkylphenols and ethylene oxide/propylene oxide copolymers and mixtures of the foregoing.

5. The composition of Preferred 4 wherein the disintegrant(s) is cross-linked polyvinyl pyrrolidone or cross-linked sodium carboxymethyl cellulose.

6. The composition of Preferred 5 wherein the dispersant is a napthalene-sulfonate-formaldehyde condensate or a ligninsulfonate.

7. The composition of Preferred 4 wherein the heat activated binder(s) is a block copolymer of ethylene oxide/propylene oxide where 80% is ethylene oxide and 20% is propylene oxide, or polyethoxylated dinonylphenol with 150 ethylene oxide units.

8. The composition of Preferred 3 wherein the water soluble diluent is urea or sorbitol.

9. The composition of Preferred 8 wherein the active ingredient is N'(3,4-dichlorophenyl)-N,N-dimethyl urea (diuron) .

10. The composition of Preferred 8 wherein the active ingredient is methyl 2-benzimidazole-carbamate (carbendazim).

11. The composition of Preferred 8 wherein the active ingredient is 3-cyclohexyl-6-dimethylamino-1-methyl-1,3,5-triazin-2,4-(1H,3H)dione (hexazinone).

12. The composition of Preferred 8 wherein the active ingredient is selected from:

methyl 2-[[[[(4,6-dimethyl-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate;

methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-2-thiophenecarboxylate;

2-chloro-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]-benzene-sulfonamide;

ethyl 2-[[[[(4-chloro-6-methoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate;

methyl 2-[[[[(4-methyl-6-methoxy-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]benzoate;

2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-N, N-dimethyl-3-pyridinecarboxamide;

methyl 2-[[[[[4-ethoxy-6-(methylamino-1,3,5-triazin-2-yl]amino]carbonyl]amino]sulfonyl]benzoate;

methyl 2-[[[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylamino]carbonyl]amino]sulfonyl]benzoate;

methyl 2-[[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]methyl]benzoate;

N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-3-(ethylsulfonyl)-2-pyridine sulfonamide;

methyl 2-[[[[[4,6-bis(difluoromethoxy)-2-pyrimidinyl]amino]carbonyl]amino]sulfonyl]benzoate;

2-(2-chloroethoxy)-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzene sulfonamide;

ethyl 5-[[[(4,6-dimethoxy-2-pyrimidinyl)-amino]carbonyl]amino]sulfonyl]-1-methyl-1H-pyrazole-4-carboxylate; or

N-[[(4,6-dimethoxy-2-pyrimidinyl) amino]carbonyl]-1-methyl-4-(2-methyl-2H-tetrazol-5-yl)-1H-pyrazole-5-sulfonamide.

DETAILED DESCRIPTION OF THE INVENTION

Compositions for agricultural or pesticidal use are usually manufactured and sold as liquid or solid concentrates. In recent years fromulations based on water-dispersible granules have become increasingly popular because they offer several advantages over other types of agricultural formulations. For example, they are stable during storage and transport. Often this is a concern with aqueous suspension concentrates that can settle or develop crystals in storage if the active ingredient has sufficient water solubility. Also, aqueous suspension concentrates are not suitable for active ingredients which are subject to aqueous hydrolysis. This is not a problem with water-dispersible granules. In comparison to wettable powders, water-dispersible granules are convenient to handle and measure and are relatively dust-free. They avoid the skin-toxicity and odor problems associated with solvent-based formualtions such as emulsion concentrates and organic suspension concentrates.

To make water-dispersible granules useful for application they are usually diluted in a mix tank containing water to form a solution or dispersion which can be sprayed. The dispersed particles formed on dilution should be no larger than 50 microns in their largest dimension to avoid nozzle pluggage or premature settling which results in uneven application of the pesticide. It is therefore necessary that all of the components of the formulated product rapidly and completely disperse or dissolve in the dilution water.

Conventional methods for preparing water-dispersible granule compositions involve (1) water-spraying in fluidized bed or pan granulation equipment (2) spray-drying (3) dry compaction and (4) extrusion of a water-wet paste. Granules prepared by fluid-bed, spray-drying or pan granulation can be formulated to disperse rapidly when diluted in water. However these processes require specialized technology including extensive dust collection systems and a space-consuming and expensive drying operation. Dry compaction and extrusion generally do not produce fast-dispersing granules, and wet-extrusion also requires a drying step.

The present invention comprises water-dispersible granular compositions which are made by extruding a dry premix through a die or screen at elevated temperature and chopping or grinding the extruded material to form granules. Advantages of these heat extruded granular compositions include (1) rapid disintegration and good dispersion properties in water (2) good attrition resistance (3) more uniform size and bulk density than granules prepared by fluid-bed or pan granulation, or by other tumbling/mixing processes such as in a rotating drum granulator (4) a simple process which uses readily available commercial extruding equipment, and (5) no need for drying or dust collection equipment.

The compositions of this invention are prepared as follows. An extrudable premix is prepared by combining the pesticidal particles with one or more water-soluble diluents, and preferably one or more water-soluble heat activated binders which soften or melt in the desired temperature range. Other additives included in the premix are wicking or swelling disintegrants and one or more dispersants. Particulate additives such as wetting agents, gas-generating agents, anticaking agents, chemical stabilizers, and inert fillers may optionally be added.

The process of the invention comprises extruding a dry premix comprising by weight based on the total weight of the composition:

1) 0.01-90% of one or more active ingredients;

2) 1-60% of one or more water-soluble diluents;

3) 0-30% of one or more water-soluble heat activated binders that melt at temperatures between 40°-120° C.; and

4) two or more additives selected from the group consisting of:

a) 0-10% anticaking agent(s);

b) 0-10% chemical stabilizer(s);

c) 0-20% gas generating agents;

d) 0.1-10% wicking or sweliling disintegrant(s);

e) 0.1-20% dispersant(s);

f) 0-5% wetting agent(s); and

g) 0-80% inert filler(s);

through a die or screen at a temperature from 50° C. to 130° C. and chopping or milling the extruded material to form uniform granules.

The preferred embodiments of the process of the invention include the preferred conditions for the compositions recited above and a temperature of from 75° C. to 115° C.

The premix is blended and milled to an average particle diameter between 1 and 50 microns. Preferably, the premix is fed or metered to an extruder that has been heated electrically, by steam, or by other conventional means of heating. Suitable extruders include axial and radial designs with single or twin screws, and roll-type extrusion presses. In some types of extrusion equipment, for example, a California Pellet Mill, the heat can be generated from friction. Other means of heating the premix could include preheating the premix before extrusion, or heating the individual components of the premix before blending. The premix is heated to or maintained at a temperature in the range of about 50° C. to 130° C., preferably about 75° C. to 115° C. The optimum temperature will vary with the composition, but can be determined empirically.

The heated premix is extruded through a die or screen. The die holes range in diameter from 0.25 mm to 7 mm, preferably from 0.4 mm to 2 mm. Depending on the composition and the type of extruder used, the extruded material might be recycled until the strands are uniform in texture. Generally the extruded material is allowed to cool to harden and reduce stickiness, although this may not be necessary. The strands are chopped, milled or rolled and then screened to approximately 10 to 60 U.S. mesh size granules. A narrower cut size range may be selected. In some cases the strands may be sufficiently brittle so that they break on their own into short lengths.

The active ingredient should be chemically stable in the extrusion temperature range. Examples of suitable active ingredients are listed in Table 1.

                                      TABLE 1                                      __________________________________________________________________________     Cmpd.                                                                          No. Common Name                                                                             m.p. (°C.)                                                                     Chemical Name                                              __________________________________________________________________________     HERBICIDES                                                                      1  acifluorfen                                                                             142-160                                                                               5-[2-chloro-4-(trifluoro                                                       methyl)phenoxy]-2-nitro-                                                       benzoic acid                                                2  asulam   142-144                                                                               methyl [(4-aminophenyl)-                                                       sulfonyl]carbamate                                          3  atrazine 175-177                                                                               6-chloro-N-ethyl-N'-(1-                                                        methylethyl)-1,3,5-                                                            triazine-2,4-diamine                                        4  bensulfuron                                                                             185-188                                                                               2-[[[[(4,6-dimethoxy-2-                                        methyl          pyrimidinyl)amino]-                                                            carbonyl]amino]sulfonyl]-                                                      methyl]benzoic acid,                                                           methyl ester                                                5  bentazon 137-139                                                                               3-(1-methylethyl)-(1H)-                                                        2,1,3-benzothiadiazin-4                                                        (3H)-one, 2,2-dioxide                                       6  bromacil 158-159                                                                               5-bromo-6-methyl-3-(1-                                                         methylpropyl)-2,4(1H,3H)                                                       pyrimidinedione                                             7  bromoxynil                                                                              194-195                                                                               3,5-dibromo-4-hydroxy-                                                         benzonitrile                                                8  chloramben                                                                              200-201                                                                               3-amino-2,5-dichloro-                                                          benzoic acid                                                9  chlorimuron                                                                             >100   2-[[[[(4-chloro-6-methoxy-                                     ethyl           2-pyrimidinyl)amino]                                                           carbonyl]-amino]sulfonyl]                                                      benzoic acid, ethyl ester                                  10  chloroxuron                                                                             151-152                                                                               N'-[4-(4-chlorophenoxy)-                                                       phenyl]N,N-dimethylurea                                    11  chlorsulfuron                                                                           174-178                                                                               2-chloro-N-[[(4-methoxy-6-                                                     methyl-1,3,5-triazin-2-yl)-                                                    amino]carbonyl]benzene-                                                        sulfonamide                                                12  chlortoluron                                                                            147-148                                                                               N'-(3-chloro-4-methylphenyl)-                                                  N,N-dimethylurea                                           13  clomazone                                                                               oil    2-[(2-chlorophenyl)methyl]-                                                    4,4-dimethyl-3-isoxazoli-                                                      dinone                                                     14  cyanazine                                                                               166-167                                                                               2-[[4-chloro-6-(ethylamino)-                                                   1,3,5-triazin-2-yl]amino]-                                                     2-methylpropanenitrile                                     15  dazomet  104-105                                                                               tetrahydro-3,5-dimethyl-2H-                                                    1,3,5-thiadiazine-2-thione                                 16  desmediphan                                                                             120    ethyl [3-[[(phenylamino)-                                                      carbonyl]oxy]phenyl]-                                                          carbamate                                                  17  dicamba  114-116                                                                               3,6-dichloro-2-methoxybenzoic                                                  acid                                                       18  dichlobenil                                                                             139-145                                                                               2,6-dichlorobenzonitrile                                   19  dichlorprop                                                                             117-118                                                                               (±)-2-(2,4-dichlorophenoxy)-                                                propanoic acid                                             20  diphenamid                                                                              134-135                                                                               N,N-dimethyl-α-phenylbenzene-                                            acetamide                                                  21  dipropetryn                                                                             104-106                                                                               6-(ethylthio)-N,N'-bis(1-                                                      methylethyl)-1,3,5-                                                            triazine-2,4-diamine                                       22  diuron   158-159                                                                               N'-(3,4-dichlorophenyl)-N,N-                                                   dimethylurea                                               23  thiameturon                                                                             >100   3-[[[[(4-methoxy-6-methyl-                                                     1,3,5-triazin-2-yl)amino]-                                                     carbonyl]amino]sulfonyl]-                                                      2-thiophenecarboxylic acid,                                                    methyl ester                                               24  --       >100   2-[[[N-(4-methoxy-6-methyl-                                                    1,3,5-triazine-2-yl)-N-                                                        methylamino]carbonyl]-                                                         amino]sulfonyl] benzoic                                                        acid, methyl ester                                         25  fenac    156    2,3,6-trichlorobenzeneacetic                                                   acid                                                       26  fenuron  133-134                                                                               N,N-dimethyl-N'-phenylurea                                 27  fluometuron                                                                             163-164                                                                               N,N-dimethyl-N'-[3-(trifluoro-                                                 methyl)phenyl]urea                                         28  fluridone                                                                               151-154                                                                               1-methyl-3-phenyl-5-[3-(tri-                                                   fluoromethyl)phenyl]-                                                          4(1H)-pyridinone                                           29  fomesafen                                                                               220-221                                                                               5-[2-chloro-4-(trifluoro-                                                      methyl)phenoxy]-N-(methyl-                                                     sulfonyl)-2-nitrobenzamide                                 30  glyphosate                                                                              200    N-(phosphonomethyl)glycine                                 31  hexazinone                                                                              115-117                                                                               3-cyclohexyl-6-(dimethyl-                                                      amino)-1-methyl-1,3,5-                                                         triazine-2,4(1H,3H)-dione                                  32  imazamethabenz                                                                          >100   6-(4-isopropyl-4-methyl-                                                       5-oxo-2-imidazolin-2-yl)-                                                      m-toluic acid, methyl ester                                                    and 6-(4-isopropyl-4-methyl-                                                   5-oxo-2-imidazolin-2-yl)-                                                       -p-toluic acid, methyl ester                              33  imazaquin                                                                               219-222                                                                               2-[4,5-dihydro-4-methyl-4-                                                     (1-methylethyl)-5-oxo-1H-                                                      imidazol-2-yl]-3-quinoline-                                                    carboxylic acid                                            34  imazethapyr                                                                             172-175                                                                               (±)-2-[4,5-dihydro-4-methyl-4-                                              (1-methylethyl)-5-oxo-1H-                                                      imidazol-2-yl)-5-ethyl-                                                        3-pyridinecarboxylic acid                                  35  ioxynil  209    4-hydroxy-3,5-diiodobenzo-                                                     nitrile                                                    36  isoproturon                                                                             155-156                                                                               N-(4-isopropylphenyl)-N',N'-                                                   dimethylurea                                               37  isouron  119-120                                                                               N'-[5-(1,1-dimethylethyl)-3-                                                   isoxazolyl]-N,N-dimethylurea                               38  isoxaben 176-179                                                                               N-[3-(1-ethyl-1-methylpropyl)-                                                 5-isoxazolyl]-2,6-dimethoxy-                                                   benzamide                                                  39  karbutilate                                                                             176-178                                                                               3-[[(dimethylamino)carbonyl]-                                                  amino]phenyl-(1,1-dimethyl-                                                    ethyl)carbamate                                            40  lenacil  316-317                                                                               3-cyclohexyl-6,7-dihydro-1H-                                                   cyclopentapyrimidine-2,4-                                                      (3H,5H)dione                                               41  MCPA     100-115                                                                               (4-chloro-2-methylphenoxy)-                                                    acetic acid                                                42  MCPB     100    4-(4-chloro-2-methylphenoxy)-                                                  butanoic acid                                              43  mefluidide                                                                              183-185                                                                               N-[2,4-dimethyl-5-[[(tri-                                                      fluoromethyl)sulfonyl]-                                                        amino]phenyl]acetamide                                     44  methabenz-                                                                              119-120                                                                               1,3-dimethyl-3-(2-benzothia-                                   thiazuron       zolyl)urea                                                 45  methazole                                                                               123-124                                                                               2-(3,4-dichlorophenyl)-4-                                                      methyl-1,2,4-oxadiazol-                                                        idine-3,5-dione                                            46  metribuzin                                                                              125-126                                                                               4-amino-6-(1,1-dimethylethyl)-                                                 3-(methylthio)-1,2,4-                                                          triazin-5(4H)-one                                          47  metsulfuron                                                                             163-166                                                                               2-[[[[(4-methoxy-6-methyl-                                     methyl          1,3,5-triazin-2-yl)amino]-                                                     carbonyl]amino]sulfonyl]-                                                      benzoic acid, methyl ester                                 48  monuron  174-175                                                                               N'-(4-chlorophenyl)-N,N-                                                       dimethylurea                                               49  naptalam 185    2-[(1-naphthalenylamino)-                                                      carbonyl]benzoic acid                                      50  neburon  102-103                                                                               1-butyl-3-(3,4-dichloro-                                                       phenyl)-1-methylurea                                       51  nitralin 151-152                                                                               4-(methylsulfonyl)-2,6-                                                        dinitro-N,N-dipropyl-                                                          aniline                                                    52  norflurazon                                                                             174-180                                                                               4-chloro-5-(methylamino)-2-                                                    [3-(trifluoromethyl)phenyl]-                                                   3(2H)-pyridazinone                                         53  oryzalin 141-142                                                                               4-(dipropylamino)-3,5-dinitro-                                                 benzenesulfonamide                                         54  perfluidone                                                                             142-144                                                                               1,1,1-trifluoro-N-[2-methyl-                                                   4-(phenylsulfonyl)phenyl]-                                                     methanesulfonamide                                         55  phenmedipham                                                                            143-144                                                                               3-[(methoxycarbonyl)amino]-                                                    phenyl (3-methylphenyl)-                                                       carbamate                                                  56  picloram >215   4-amino-3,5,6-trichloro-2-                                              (DEC)  pyridinecarboxylic acid                                    57  prometryn                                                                               118-120                                                                               N,N'-bis(1-methylethyl)-6-                                                     (methylthio)-1,3,5-triazine-                                                   2,4-diamine                                                58  pronamide                                                                               155-156                                                                               3,5-dichloro-N-(1,1-dimethyl-                                                  2-propynyl)benzamide                                       59  propazine                                                                               212-214                                                                               6-chloro-N,N'-bis(1-methyl-                                                    ethyl)-1,3,5-triazine-                                                         2,4-diamine                                                60  pyrazon  205-206                                                                               5-amino-4-chloro-2-phenyl-                                                     3(2H)pyridazinone                                          61  siduron  133-138                                                                               N-(2-methylcyclohexyl)-N'-                                                     phenylurea                                                 62  simazine 225-227                                                                               6-chloro-N,N'-diethyl-1,3,5-                                                   triazine-2,4-diamine                                       63  sulfometuron                                                                            182-189                                                                               2-[[[[(4,6-dimethyl-2-                                         methyl          pyrimidinyl)amino]carbonyl]-                                                   amino]sulfonyl]benzoic                                                         acid, methyl ester                                         64  tebuthiuron                                                                             161-164                                                                               N-[5-(1,1-dimethylethyl)-                                                      1,3,4-thiadiazol-2-yl]-                                                        N,N'-dimethylurea                                          65  terbacil 175-177                                                                               5-chloro-3-(1,1-dimethyl-                                                      ethyl)-6-methyl-2,4(1H,3H)-                                                    pyrimidinedione                                            66  torbuthyl-                                                                              177-179                                                                               2-(tert-butylamino)-4-chloro-                                  azine           6-(ethyl-amino)- .sub.- s-triazine                         67  terbutryn                                                                               104-105                                                                               N-(1,1-dimethylethyl)-N'-                                                      ethyl-6-(methylthio)-1,3,5-                                                    triazine-2,4-diamine                                       68  triclopyr                                                                               148-150                                                                               [(3,5,6-trichloro-2-pyri-                                                      dinyl)oxy]acetic acid                                      69  2,4-D    140    (2,4-dichlorophenoxy)acetic                                                    acid                                                       70  2,4-DB   119-120                                                                               4-(2,4-dichlorophenoxy)-                                                       butanoic acid                                              71  triasulfuron                                                                            >100   (3-(6-methoxy-4-methyl-1,3,5-                                                  triazin-2-yl)-1-[2-(2-                                                         chloroethoxy)phenylsulfonyl]                                                   urea                                                       72  primisulfuron                                                                           >100   [2-/3-(4,6-bis(difluoro-                                                       methoxypyrimidin-2-yl-                                                         ureidosulfonyl)benzoic                                                         acid methylester]                                          73  --       >100   [2-/3-(4,6-bis(difluoro-                                                       methoxy)-pyrimidin-2-yl)-                                                      ureidosulfonyl)-benzoic acid                                                   methylester)                                               74  NC-311   170-172                                                                               [5-pyrazolesulfonamide, N-[(4-                                                 methoxy-6-methyl-                                                              pyrimidine-2-yl)-amino-                                                        carbonyl]-4-methoxy-                                                           carbonyl-1-methyl-]                                        75  --       160-162                                                                               N-[[(4,6-dimethoxy-2-                                                          pyrimidinyl)amino]carbonyl]-                                                   3-(ethylsulfonyl)-2-                                                           pyridinesulfonamide                                        76  --       152-159                                                                               2-[[[[(4,6-dimethoxy-2-                                                        pyrimidinyl)amino]carbonyl]-                                                   amino]sulfonyl]-N,N-                                                           dimethyl-3-pyridine-                                                           carboxamide                                                77  --       204-206                                                                               Methyl 2-[[[[[4-ethoxy-6-                                                      (methylamino)-1,3,5-triazin-                                                   2-yl]amino]carbonyl]amino]-                                                    sulfonyl]benzoate                                          FUNGICIDES                                                                     78  carbendazim                                                                             302-307                                                                               methyl 2-benzimidazole-                                                        carbamate                                                  79  thiuram  146    tetramethylthiuram disulfide                               80  dodine   136    n-dodecylguanidine acetate                                 81  chloroneb                                                                               133-135                                                                               1,4-dichloro-2,5-dimethoxy-                                                    benzene                                                    82  cymoxanil                                                                               160-161                                                                               2-cyano-N-ethylcarbamoyl-                                                      2-methoxyiminoacetamide                                    83  captan   178    N-trichloromethylthiotetra-                                                    hydrophthalamide                                           84  folpet   177    N-trichloromethylthio-                                                         phthalimide                                                85  thiophanate-                                                                            195    dimethyl 4,4'-(o-phenylene)-                                   methyl          bis(3-thioallophanate)                                     86  thiabendazole                                                                           304-305                                                                               2-(thiazol-4-yl)benzimida-                                                     zole                                                       87  chlorothalonil                                                                          240-241                                                                               tetrachloroisophthalo-                                                         nitrile                                                    88  dichloran                                                                               195    2,6-dichloro-4-nitroaniline                                89  captafol 160-161                                                                               cis-N-[1,1,2,2-tetrachloro-                                                    ethyl)thio]cyclohex-4-                                                         ene-1,2- dicarbioximide                                    90  iprodione                                                                               133-136                                                                               3-(3,5-dichlorophenyl)-N-                                                      (1-methylethyl)-2,4-                                                           dioxo-1-imidazolidine                                                          carboxamide                                                91  vinclozolin                                                                             108    3-(3,5-dichlorophenyl)-5-                                                      ethenyl-5-methyl-2,4-                                                          oxazolidinedione                                           92  kasugamycin                                                                             202-204                                                                               kasugamycin                                                             (DEC)                                                             93  triadimenol                                                                             121-127                                                                               beta-(4-chlorophenoxy)-α-                                                (1,1-dimethylethyl)-1-H-                                                       1,2,4-triazol-1-ethanol                                    94  flutriafol                                                                              130    +-α-(2-fluorophenyl-α-(4-                                          fluorophenyl)-1H-1,2,4-                                                        triazole-1-ethanol                                         95  flusilazol                                                                               52-53 1-[[bis(4-fluorophenyl)-                                                HCl 201-203                                                                           methylsilyl)methyl]-1H-                                                        1,2,4-triazole                                             96  hexaconazole                                                                            111    (+/-)-α-butyl-α-(2,4-di                                            chlorophenyl)-1H-1,2,4-                                                        triazole-1-ethanol                                         97  fenarimol                                                                               117-119                                                                               α-(2-chlorophenyl)-α(4-                                            chlorophenyl)-5-pyri-                                                          dinemethanol                                               BACTERICIDES                                                                   98  oxytetracycline                                                                         181-182                                                                               oxytetracycline dihydrate                                      dihydrate                                                                               (DEC)                                                             ACARICIDES                                                                     99  hexathiazox                                                                             108-109                                                                               trans-5-(4-chlorophenyl)-N-                                                    cyclohoxyl-4-methyl-2-oxo-3-                                                   thiazolidinecarboxamide                                    100 oxythioquinox                                                                           169-170                                                                               6-methyl-1,3-dithiolo-                                                         [2,3-B]quinonolin-2-one                                    101 dienochlor                                                                              122-123                                                                               bis(pentachloro-2,4-cyclo-                                                     pentadien-1-yl)                                            102 cyhexatin                                                                               245    tricyclohexyltin hydroxide                                 103 fenbutatin oxide                                                                        145    bis(tris(2-methyl-2-phenyl-                                                    propyl)tin] oxide                                          INSECTICIDES                                                                   104 carbofuran                                                                              150-152                                                                               methylcarbamic acid, ester                                                     with 2,3-dihydro-2,2-di-                                                       methyl-7-benzofuranol                                      105 carbaryl 142    methylcarbamic acid, ester                                                     with a-naphthol                                            106 thiodicarb                                                                              173-174                                                                               dimethyl N,N'-[thiobis-                                                        (N-methylimmo)carbonyl-                                                        oxy]]-bis[ethanimido-                                                          thioate]                                                   107 deltamethrin                                                                             98-101                                                                               α-cyano-3-phenoxybenzyl-cis-                                             3-(2,2-dibromovinyl)-2,2-                                                      dimethylcyclopropane                                                           carboxylate                                                108 tetrachlorvinphos                                                                        93-98 (Z)-2-chloro-1-(2,4,5-tri-                                                     chlorophenyl)vinyl dimethyl                                                    phosphate                                                  __________________________________________________________________________

The compositions of this invention contain at least one water-soluble diluent. This is defined as a water-soluble polymer, salt, surfactant, hydrated organic or inorganic compound or carbohydrate which melts or softens at elevated temperatures and acts as the primary extrusion aid. It has been discovered that, in some cases, a suitable water-soluble diluent may have a melting point significantly higher than the extrusion temperature but it will nevertheless function as an effective extrusion aid. Apparently it forms a lower melting eutectic mixture with other soluble ingredients in the composition. For example, urea has a sharp melting point at 133° C. which is higher than typical extrusion temperatures. Napthalene sulfonates and their condensates, which are well known in the art as dispersants and wetting agents for agricultural formulations, have no melting point. However, a mixture of the two in the presence of residual moisture in the composition, will soften at temperatures as low as 80° C. making the urea an effective extrusion aid. Some non-limiting examples of suitable water-soluble diluents are hydroxyethylcellulose, sorbitol, lactose, urea, ethylurea, polyvinyl alcohol and sodium acetate trihydrate.

In a preferred embodiment, the compositions of this invention include a heat activated binder along with the water soluble diluent. The heat-activated binder (HAB) is a solid, surface active material which dissolves rapidly in water, has some viscosity near its melting point, and is capable of acting as a binder and extrusion aid when heat is applied. At an elevated temperature the binder softens and melts, thereby becoming sticky enough to bind the pesticidal particles into larger aggregates. It is theorized that the softened or melted HAB can also function as a plastic or viscoelastic lubricant allowing the composition to extrude more easily through a die or screen. The preferred melting point range for the HAB is 45° C. to 100° C. Examples of suitable HABs, which are not intended to be limiting, are ethylene oxide/propylene oxide copolymers, polyethoxylated alkylphenols, polyethoxylated fatty acids or alcohols and polyethylene glycol. Preferred HAB's are ethylene oxide/propylene oxide copolymers and polyethoxylated alkylphenols. Most preferred are block copolymers of ethylene oxide/propylene oxide where 80% is ethylene oxide and 20% is propylene oxide, and polyethoxylated dinonyl phenol with approximately 150 moles of ethylene oxide.

The composition also contains disintegrant(s) which wick in water and physically expand to aid break-up of the granule. Non-limiting examples of suitable disintegrants include starch, cross-linked polyvinylpyrrolidone, microcrystalline cellulose, cross-linked sodium carboxymethyl cellulose, sodium starch glycolate, soy polysaccharide and ion exchange resins. Cross-linked polyvinylpyrrolidone and cross-linked sodium carboxymethyl cellulose are preferred.

Dispersant(s) are needed to help disperse the active ingredient in water. Non-limiting examples of suitable dispersants include sodium and ammonium salts of napthalene sulfonate-formaldehyde condensates; sodium, calcium and ammonium salts of ligninsulfonates (optionally polyethoxylated); sodium and ammonium salts of maleic anhydride copolymers and sodium salts of condensed phenolsulfonic acid.

Optional additives include:

(1) Anticaking agents to prevent clumping of granules when stored under hot warehouse conditions. Non-limiting examples include sodium and ammonium phosphates, sodium carbonate and bicarbonate, sodium acetate, sodium metasilicate, magnesium, zinc and calcium sulfates, magnesium hydroxide, (all optionally as hydrates), anhydrous calcium chloride, molecular sieves, sodium alkylsulfosuccinates, calcium and barium oxides.

(2) Chemical stabilizers to prevent decomposition of the active(s) during storage. Non-limiting examples of suitable chemical stabilizers include alkaline earth and transition metal sulfates such as magnesium, zinc, aluminum and iron; sodium hexametaphosphate, calcium chloride and boric anhydride.

(3) Gas producing disintegrants for faster breakup of the granule in water. Non-limiting examples of suitable gas generating additives are combinations of sodium and potassium bicarbonates and carbonates with acids such as citric and fumaric acid.

(4) Wetting agents to improve the speed of wetting upon mixing with water. Non-limiting examples of suitable anionic wetting agents include sodium salts of alkyl napthalene sulfonates, alkyl benzene sulfonates, alkyl sulfosuccinates, taurates, alkyl sulfates and phosphate esters. Examples of suitable nonionic wetting agents include acetylenic diols and alkyl phenol ethoxylates.

(5) Inert fillers, including but not limited to inorganic fillers well known in the art. Non-limiting examples are swelling and non-swelling clays, synthetic and diatomaceous silicas, calcium and magnesium silicates, titanium dioxide, aluminum, calcium and zinc oxide, calcium and magnesium carbonate, ammonium, sodium, potassium, calcium and barium sulfate, charcoal.

The granules of this invention beak up rapidly and form high quality dispersions in water as determined from the Long Tube Sedimentation test described in U.S. Pat. No. 3,920,442 col.9, lines 1 to 39. Acceptable Long Tube Sedimentation values correspond to 0.02 ml, preferably 0.01 ml of solids after 5 minutes of settling. The granules should exhibit low attrition characteristics which can be determined by the attrition test in U.S. Pat. No. 3,920,442 col 8, lines 5 to 48. The test is modified to use test samples of the appropriate granule size (e.g. 14-20 U.S. mesh). Attrition values of less than 40% and preferably less than 30% are acceptable.

The following examples are presented to illustrate, but not to restrict, this invention.

    ______________________________________                                         Identity of Ingredients Used in Examples                                       Name            Identity                                                       ______________________________________                                         Macol ® DNP150                                                                             Polyethoxylated dinonylphenol                                  (Mazer Chemicals)                                                                              (150 moles ethylene oxide)                                     Pluronic ® F108                                                                            80% Ethylene oxide/20%                                         propylene       oxide block copolymer                                          (BASF Corp)                                                                    Polyplasdone ® XL-10                                                                       Crosslinked polyvinyl                                          (GAF Corp)      pyrrolidone                                                    Lomar ® PWA Ammonium napthalene sulfonate-                                 (Henkel Corp)   formaldehyde condensate                                        Morwet ® EFW                                                                               Mixture of alkyl carboxylate                                   (Witco Corp)    and Sodium alkyl napthalene                                                    sulfonate                                                      ______________________________________                                    

EXAMPLE 1

A 150 gm premix was formulated from the ingredients listed below. The ingredients were blended and then passed through a MikroPulverizer hammer mill. The milled premix was slowly added to a 1 inch Wayne single screw extruder with a 25:1 L/D ratio. The extruder had three electrical heating zones along the barrel plus a band heater for the die. Temperatures were generally kept as uniform as possible along the barrel and the die. A mechanical or electronic pressure indicator was fitted near the end of the barrel to measure hydraulic pressures close to the die.

The premix was extruded through a die containing 8×1 mm holes arranged in a circular pattern. The extruded product was allowed to cool for a few minutes then it was chopped up in a small food processor and screened to obtain the 14 to 35 U.S. sieve cut size.

Extruder temperature range 87°-91° C.

Hydraulic pressure range 0-50 psi

    ______________________________________                                         Premix Formulation                                                             ______________________________________                                                            Weight Percent                                              ______________________________________                                         Diuron technical   62.4                                                        Lomar ® PWA    10.0                                                        Macol ® DNP150 5.0                                                         Morwet ® EFW   2.0                                                         Polyplasdone ® XL-10                                                                          2.0                                                         Urea               18.6                                                        ______________________________________                                                            Properties of Granules                                      ______________________________________                                         Long Tube Sedimentation                                                                           .002                                                        Long Tube Sedimentation after                                                                     .002                                                        aging 2 weeks @ 54 C.                                                          % Attrition (14-20 mesh cut)                                                                      1.7                                                         Bulk Density (lb/cu ft)                                                                           39.8                                                        ______________________________________                                    

EXAMPLE 2

The procedure of Example 1 was used with the following premix. The die had 6×1 mm holes arranged in a hexagonal pattern.

Extrusion temperature range 88°-94° C.

Hydraulic pressure range 0-1000 psi

    ______________________________________                                         Premix Formulation                                                             ______________________________________                                                            Weight Percent                                              ______________________________________                                         Diuron technical   62.4                                                        Lomar ® PWA    7.0                                                         Pluronic ® F108                                                                               5.0                                                         Polyplasdone ® XL-10                                                                          2.0                                                         Citric acid anhydrous                                                                             2.0                                                         Sodium bicarbonate 3.0                                                         Urea               18.6                                                        ______________________________________                                                            Properties of Granules                                      ______________________________________                                         Long Tube Sedimentation                                                                           .002                                                        Long Tube Sedimentation after                                                                     trace                                                       aging 2 weeks @ 54 C.                                                          % Attrition (14-20 mesh cut)                                                                      8.7                                                         Bulk Density (lb/cu ft)                                                                           25.1                                                        ______________________________________                                    

EXAMPLE 3

The procedure of example 2 was used with the following premix.

Extrusion temperature range 88°-94° C.

Hydraulic pressure range 300-500 psi

Screw speed 26 rpm

    ______________________________________                                         Premix Formulation                                                             ______________________________________                                                            Weight Percent                                              ______________________________________                                         Diuron technical   62.4                                                        Lomar ® PWA    7.0                                                         Macol ® DNP150 5.0                                                         Polyplasdone ® XL-10                                                                          2.0                                                         Citric acid anhydrous                                                                             5.0                                                         Sodium carbonate anhydrous                                                                        4.0                                                         Urea               14.6                                                        ______________________________________                                                            Properties of Granules                                      ______________________________________                                         Long Tube Sedimentation                                                                           trace                                                       Long Tube Sedimentation after                                                                     .002                                                        aging 2 weeks @ 54 C.                                                          % Attrition (14-20 mesh cut)                                                                      8.3                                                         Bulk density (lb/cu ft)                                                                           23.9                                                        ______________________________________                                    

EXAMPLE 4

The procedure of example 2 was used with the following premix:

Extrusion temperature range 86°-91° C.

Hydraulic pressure range 100-300 psi

Screw speed 26 rpm

    ______________________________________                                         Premix Formulation                                                             ______________________________________                                                            Weight Percent                                              ______________________________________                                         Diuron technical   62.4                                                        Lomar ® PWA    7.0                                                         Macol ® DNP150 5.0                                                         Polyplasdone ® XL-10                                                                          2.0                                                         Citric acid anhydrous                                                                             5.0                                                         Sodium carbonate anhydrous                                                                        4.0                                                         Calcium sulfate anhydrous                                                                         3.0                                                         Urea               11.6                                                        ______________________________________                                                            Properties of Granules                                      ______________________________________                                         Long Tube Sedimentation                                                                           0                                                           Long Tube Sedimentation after                                                                     .002                                                        aging 2 weeks @ 54 C.                                                          % Attrition (14-20 mesh cut)                                                                      6.7                                                         Bulk density (lb/cu ft)                                                                           24.8                                                        ______________________________________                                    

EXAMPLE 5

The procedure of Example 2 was used with the following premix:

Extrusion temperature range 84°-92° C.

Hydraulic pressure range 100-300 psi

Screw speed 30 rpm

    ______________________________________                                         Premix Formulation                                                             ______________________________________                                                            Weight Percent                                              ______________________________________                                         Methyl 2-[[[[(4-methyl-6-                                                                         52.0                                                        methoxy-1,3,5-triazin-2-                                                       yl)amino]carbonyl]amino]-                                                      sulfonyl]benzoate                                                              Lomar ® PWA    7.0                                                         Pluronic ® F108                                                                               8.0                                                         Polyplasdone ® XL-10                                                                          2.0                                                         Citric Acid anhydrous                                                                             1.0                                                         Sodium bicarbonate 1.5                                                         Sorbitol           28.5                                                        ______________________________________                                                            Properties of Granules                                      ______________________________________                                         Long Tube Sedimentation                                                                           trace                                                       Long Tube Sedimentation after                                                                     .004                                                        aging 2 weeks @ 54 C.                                                          % Attrition (14-20 mesh cut)                                                                      0.7                                                         Bulk density (lb/cu ft)                                                                           39.6                                                        ______________________________________                                    

EXAMPLE 6

The procedure of Example 2 was used with the following premix. 200 gm of premix was prepared for extrusion.

Extrusion temperature range 84°-87° C.

Screw speed 30 rpm

    ______________________________________                                         Premix Formulation                                                             ______________________________________                                                            Weight Percent                                              ______________________________________                                         Methyl 2-[[[[(4-methyl-6-                                                                         52.0                                                        methoxy-1,3,5-triazin-2-                                                       yl)amino]carbonyl]amino]-                                                      sulfonyl]benzoate                                                              Lomar ® PWA    7.0                                                         Pluronic ® F108                                                                               8.0                                                         Polyplasdone ® XL-10                                                                          2.0                                                         Citric acid anhydrous                                                                             1.0                                                         Sodium bicarbonate 1.5                                                         Type 4A molecular sieve                                                                           4.0                                                         (pulverized)                                                                   Sorbitol           24.5                                                        ______________________________________                                                            Properties of Granules                                      ______________________________________                                         Long Tube Sedimentation                                                                           .002                                                        Long Tube Sedimentation                                                                           .003                                                        after 2 weeks @ 54° C.                                                  Bulk density (lb/cu ft)                                                                           39.0                                                        ______________________________________                                     

What is claimed is:
 1. Water-dispersible granular compositions made by extruding at elevated temperature a dry premix comprising by weight based on the total weight of the composition:1) 0.01-90% of one or more active ingredients which are stable at the extrusion temperature; 2) 1-60% of one or more water-soluble diluents; 3) an effective amount of one or more water-soluble heat activated binders that melt at temperatures between 40°-120° C.; and 4) two or more additives selected from the group consisting of:a) up to 10% anti caking agent(s); b) up to 10% chemical stabilizer(s); c) up to 20% gas generators; d) 0.1-10% disintegrant(s); e) 0.1-20% dispersant(s); f) up to 5% wetting agent(s); and g) up to 80% inert filler(s);and the sum of all the ingredients in a composition is 100%.
 2. The composition of claim 1 wherein the active ingredient(s) comprise 10-70%, and the heat activated binder(s) comprise 1-30%.
 3. The composition of claim 1 wherein the active ingredient(s) comprise 10-70%, and the heat activated binder(s) comprise 1-15%.
 4. The composition of claim 3 wherein the heat activated binder(s) is selected from the group consisting of polyethoxylated dinonylphenol, ethylene oxide/propylene oxide copolymer and mixtures of the foregoing.
 5. The composition of claim 4 wherein the water soluble diluent is urea, ethylurea, sorbitol, lactose or sodium acetate trihydrate and mixtures thereof.
 6. The composition of claim 5 wherein the ethylene oxide/propylene oxide copolymer if present is about 80% ethylene oxide and 20% propylene oxide and the polyethoxylated dinonylphenol has 150 ethylene oxide units.
 7. The composition of claim 5 wherein the water soluble diluent is urea or sorbitol.
 8. The composition of claim 7 wherein the active ingredient is selected from the group consisting ofmethyl 2-[[[[(4,6-dimethyl-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate; methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-2-thiophenecarboxylate; 2-chloro-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]-benzene-sulfonamide; ethyl 2-[[[[(4-chloro-6-methoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate; methyl 2-[[[[(4-methyl-6-methoxy-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]benzoate; 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-N, N-dimethyl-3-pyridinecarboxamide; methyl 2-[[[[[4-ethoxy-6-(methylamino-1,3,5-triazin-2-yl]amino]carbonyl]amino]sulfonyl]benzoate; methyl 2-[[[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylamino]carbonyl]amino]sulfonyl]benzoate; methyl 2-[[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]methyl]benzoate; N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-3-(ethylsulfonyl)-2-pyridine sulfonamide; methyl 2-[[[[[4,6-bis(difluoromethoxy)-2-pyrimidinyl]amino]carbonyl]amino]sulfonyl]benzoate; 2-(2-chloroethoxy)-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzene sulfonamide; ethyl 5-[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-1-methyl-1H-pyrazole-4-carboxylate; and N-[[(4,6-dimethoxy-2-pyrimidinyl) amino]carbonyl]-1-methyl-4-(2-methyl-2H-tetrazol-5-yl)-1H-pyrazole-5-sulfonamide.
 9. A process comprising extruding a dry premix of the composition of any one of claims 1-7 through a die or screen at a temperature from 50° C. to 130° C. to form granules.
 10. The composition of claim 1 wherein the water-soluble diluent(s) is selected from the group consisting of hydroxyethylcellulose, sorbitol, lactose, urea, ethylurea, polyvinyl alcohol and sodium acetate trihydrate. 